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Publication numberUS4139548 A
Publication typeGrant
Application numberUS 05/888,315
Publication dateFeb 13, 1979
Filing dateMar 20, 1978
Priority dateOct 20, 1977
Publication number05888315, 888315, US 4139548 A, US 4139548A, US-A-4139548, US4139548 A, US4139548A
InventorsKyoichi Tanaka, Kouzou Takahashi, Mitsuhiro Kanada, Toshiharu Yoshikawa
Original AssigneeToyo Contact Lens Co., Ltd.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Methyldi(trimethylsiloxy)sylylpropylglycerol methacrylate
US 4139548 A
Abstract
A novel methacrylic acid ester derivative, methyldi(trimethylsiloxy)sylylpropylglycerol methacrylate which is availably employed as a main monomer for preparing copolymers useful as a material of contact lenses. The derivative has siloxane bond which contributes to increase of the oxygen permeability of its copolymers, and has hydrophilic hydroxyl group and ether bond by which the derivative is miscible with a hydrophilic monomer in all proportions and is easily copolymerizable therewith and colorless transparent copolymers are obtained.
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Claims(1)
What we claim is:
1. A compound of the formula: ##STR3##
Description
BACKGROUND OF THE INVENTION

The present invention relates to a novel compound, and more particularly to methyldi(trimethylsiloxy)sylylpropylglycerol methacrylate which is availably employed as a main monomer for preparing copolymers useful as a material of contact lenses.

Contact lenses made of polymethyl methacrylate are well known. These contact lenses have the disadvantages that the oxygen permeability is low and the hydrophilic property is poor. Therefore, since cornea is easy to fall into a state of oxygen starvation, and also since the contact lens lacks in affinity for cornea and gives a foreign body sensation, it takes about one month for accomodation and even if persons have accomodated to wear of the contact lenses, they cannot wear over 12 hours in a day.

In order to eliminate such disadvantages of the contact lenses made of polymethyl methacrylate, there have been proposed high water content lenses made of a polymer of ethylene glycol monomethacrylate as a main component. These contact lenses have a higher oxygen permeability than that of the contact lenses made of polymethyl methacrylate, but cannot permeate a sufficient amount of oxygen for cornea. Also, these contact lenses have the fatal disadvantage of being contaminated by bacteria, because the water content is too high.

OBJECTS OF THE INVENTION

It ia an object of the present invention to provide a novel methacrylic acid ester derivative which can be availably employed as a monomer for preparing copolymers useful as a material of contact lenses.

A further object of the invention is to provide a polymerizable compound having a siloxane bond which contributes to increase of the oxygen permeability of obtained polymers.

A still further object of the invention is to provide a copolymerizable compound having the excellent miscibility with a hydrophilic monomer.

Another object of the invention is to provide a copolymerizable compound suited for preparing contact lenses which have the excellent oxygen permeability and the affinity for cornea and can be worn continuously for a long term without giving a foreign body sensation.

These and other objects of the invention will become apparent from the description hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the infrared absorption spectrum of the compound of the present invention; and

FIG. 2 is the gas chromatogram of the compound of the present invention.

DETAILED DESCRIPTION

It has now been found that the above-mentioned objects can be attained by a novel compound, i.e. methyldi(trimethylsiloxy)sylylpropylglycerol methacrylate having the following formula (I): ##STR1##

The novel compound of the present invention is prepared by reacting methyldi(trimethylsiloxy)sylylpropyl(oxypropylene oxide (hereinafter referred to as "SiPO") having the following formula (II): ##STR2## with methacrylic acid in the presence of a catalyst such as potassium hydroxide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride or triethylamine.

The reaction is generally carried out at a temperature of 80 to 105 C. for 6 to 8 hours. In order to prevent the polymerization of methacrylic acid, it is desirable to carry out the reaction in the presence of a polymerization inhibitor, while replacing air with nitrogen gas. Examples of the polymerization inhibitor are hydroquinone, hydroquinone monomethyl ether and sulfur, and hydroquinone is suitably employed due to the easiness of the removal after the completion of the reaction.

Although the reaction between SiPO and methacrylic acid is equimolar reaction, it is effective to employ 1.5 to 2.5 moles of methacrylic acid per mole of SiPO, since more than 99% of the employed SiPO can be made to react with methacrylic acid. In that case, excess methacrylic acid is removed by washing with an aqueous solution of sodium hydroxide after the completion of the reaction.

Since the product is a polymerizable, viscous, high-boiling material, it is difficult to utilize recrystallization or distillation procedure for purification, and the reaction product is usually purified by washing. The washing may be conducted by directly pouring an aqueous solution of sodium hydroxide to the reaction mixture, but the separation is difficult and, therefore, preferably the reaction mixture is first dissolved in n-hexane and then washed with an aqueous solution of sodium hydroxide. It is suitable to employ n-hexane in an amount of about 9 times the volume of the reaction mixture. The washing is usually conducted in a separatory funnel by employing the washing liquid in a volume approximately equal to the mixture of the reaction mixture and n-hexane. The under layer is the washing liquid which dissolves methacrylic acid and hydroquinone. After removing the under layer, the above washing procedure is repeated until no coloration based on the presence of hydroquinone is observed. In general, the above washing procedure is repeated 3 to 5 times. Since the thus washed mixture of the reaction mixture and n-hexane contains a small quantity of alkali, the mixture is further washed with water or a saline water to remove alkali. The use of a saline water is preferred, since the separation is easy. The washing with water or a saline water is repeated, usually 3 to 5 times, until the washing liquid becomes neutral. After washing the mixture, a small quantity of water included in the mixture is removed by employing a drying agent such as anhydrous sodium sulfate or Glauber's salt. After filtration, n-hexane is distilled away, for instance, by employing an evaporator. The removal of n-hexane by an evaporator is suitably carried out first by maintaining the temperature of a water bath at about 50 C., secondary at the same temperature with suction by means of an aspirator, and then at about 65 C. under a reduced pressure of 5 to 10 mmHg for about one hour by employing a vacuum pump.

The thus obtained novel compound of the present invention has the following features from the structural point of view, as is also apparent from the formula (I).

1. The compound has siloxane bond at the molecular end. The siloxane bond contributes to increase of the oxygen permeability of its copolymers.

2. The compound has double bond and, therefore, is copolymerizable with other unsaturated hydrocarbons.

3. The compound has hydroxyl group and ether bond in the molecule, which are hydrophilic. Therefore, the compound is miscible with hydrophilic monomers in all proportions and is easily copolymerizable therewith, and the obtained copolymers are colorless and transparent.

The compound of the present invention can be availably employed as a monomer for preparing copolymers useful as a material of contact lenses. When the compound of the invention is copolymerized with other particular monomers such as a hydrophilic monomer, there can be obtained copolymers suitable for use as a material of contact lenses which have the excellent oxygen permeability and the affinity for cornea and can be worn continuously for a long term without giving a foreign body sensation. For instance, when 30 to 80% of the compound of the invention is copolymerized with 5 to 30% of a hydrophilic monomer such as ethylene glycol monomethacrylate or diethylene glycol menomethacrylate, 5 to 60% of an alkyl methacrylate such as methyl methacrylate or ethyl methacrylate, and 0.5 to 15% of a cross-linking agent having at least two copolymerizable functional groups such as ethylene glycol dimethacrylate or diethylene glycol dimethacrylate (the above all % being % by weight based on the total weight of the reactants), in the presence of a radical polymerization initiator such as azobisisobutyronitrile or azobisdimethylvaleronitrile by means of a bulk polymerization, the produced copolymers have the excellent processing property upon the preparation of contact lenses therefrom, and the obtained contact lenses have a high oxygen permeability and the excellent affinity for cornea and can be worn continuously for a long term without giving a foreign body sensation.

The present invention is more particularly described and explained by means of the following Example.

EXAMPLE 1

[Preparation of methyldi(trimethylsiloxy)sylylpropylglycerol methacrylate (hereinafter referred to as "SiGMA") of the present invention]

A one liter round bottom flask equipped with a magnetic stirrer, a thermometer, a tube for introducing nitrogen gas, a dropping funnel and a reflux condenser was charged with 336 g. of SiPO, 6.9 g. of potassium hydroxide and 0.8 g. of hydroquinone, and was placed on an oil bath. With introducing nitrogen gas into the flask, 172 g. of methacrylic acid was added dropwise to the flask through the dropping funnel with stirring over about 30 minutes. The mixture was then gradually heated to 100 C. and at this temperature the reaction was carried out for about 7 hours. After the completion of the reaction, the reaction mixture was allowed to cool and filtered to remove potassium methacrylate. The filtrate was then admixed with n-hexane in an amount of about 9 times the volume of the filtrate and the mixture was washed several times with a 0.5N aqueous solution of sodium hydroxide to remove the excess methacrylic acid and hydroquinone by employing a separatory funnel, until the aqueous solution became colorless. The mixture was further washed several times with a saline water to remove sodium hydroxide remaining in the mixture. The thus washed mixture was then placed in an Erlenmeyer flask and was dehydrated by employing anhydrous sodium sulfate for a day and night. After removing anhydrous sodium sulfate by filtration, n-hexane was distilled away by an evaporator, first at 50 C., then at 50 C. with suction by an aspirator and further at 65 C. with reducing a pressure to 10 mmHg by a vacuum pump.

The thus obtained reaction product was a slightly viscous, transparent liquid. According to the quantitative analysis by gas chromatography, the purity of the obtained product was 98.7%. Also, the refractive index nD 20 of the product was 1.440. The infrared absorption spectrum of the product indicated absorptions of hydroxyl group at 3,420 cm.-1, of double bond at 1,640 cm.-1, of ester bond at 1,720 cm.-1, of Si-O-Si bond at 1,040 cm.-1 and 1,080 cm.-1, of methyl group at 2,950 cm.-1, 1,400 cm.-1 and 1,300 cm.-1, and of --Si--(CH3)3 group at 845 cm.-1 No absorption of epoxy group at 910 cm.-1 was observed. The infrared absorption spectrum and the gas chromatogram of the product are shown in FIG. 1 and FIG. 2, respectively.

The result of the elemental analysis was as follows:

Calculated for C17 H38 O6 Si3 : C 48.3%; H 9.0%

Found: C 49.7%; H 9.3%

From the above results, it was confirmed that the product was SiGMA. [Preparation of copolymer and contact lenses therefrom]

By employing the thus obtained SiGMA, a copolymer was prepared as follows:

Fifty-five grams of SiGMA, 10 g. of ethylene glycol monomethacrylate, 5 g. of ethylene glycol dimethacrylate, 30 g. of methyl methacrylate and 0.08 g. of azobisdimethylvaleronitrile were thoroughly admixed and then placed in a test tube. Under the ultraviolet irradiation, the polymerization was carried out stepwise at 15 C. for 16 hours, at 40 C. for 8 hours and at 50 C. for 8 hours, and then the ultraviolet irradiation was stopped and the thermal polymerization was further carried out stepwise at 60 C. for 24 hours, at 80 C. for 4 hours, at 100 C. for 4 hours and at 120 C. for 4 hours, to give a colorless, transparent rod.

From the thus obtained material for contact lens in the form of rod, a piece having a diameter of 15 mm. and a thickness of 0.1 mm. was obtained by mechanical processing, and the oxygen permeability was measured by an oxygen gas permeameter made by Rikaseiki Kogyo Co., Ltd. The oxygen permeability was 14.9 10-1 ml.cm./cm.2 sec.cmHg. Also, the material had a refractive index nD 20 of 1.4761 which was measured by Abbe's refractometer made by Erma Optical Works Co., Ltd., a specific gravity of 1.11 and a visible ray percent transmission of 97.8% which are measured by Double-Beam Spectro Photometer UV-210 made by Shimadzu Seisakusho Ltd. by employing the material having a thickness of 0.15 mm.

The material in the form of rod was subjected to a usual mechanical processing such as cutting, grinding and polishing to give contact lenses having a base-curve of 7.90 mm., a front-curve of 8.10 mm., a center thickness of 0.13 mm. and a size of 11.5 mm. The thus prepared contact lenses were worn on rabbit eyes continuously for 21 days. No change was observed on the eyes. Also, the contact lens had good hydrophilic property. The judgement of the hydrophilic property was conducted by immersing the contact lens in a 0.9% saline water and observing whether or not the surface of the contact lens was covered with the water when the contact lens was picked out with tweezers. When the contact lens was covered with the water, the hydrophilic property of the lens was judged as good.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3746734 *Feb 4, 1972Jul 17, 1973Gen ElectricAcrylate or methacrylate silanes
US3878263 *Jul 10, 1972Apr 15, 1975Stauffer Chemical CoAcrylate-functional polysiloxane polymers
US3965150 *Jan 13, 1975Jun 22, 1976General Electric CompanyPolyether esters of alkenoic acids
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4293678 *Nov 26, 1979Oct 6, 1981Union Carbide CorporationRadiation-curable acrylated epoxy silicone compositions
US4395496 *Nov 16, 1981Jul 26, 1983Uco Optics, Inc.Cured cellulose ester, method of curing same, and use thereof
US4558082 *May 10, 1984Dec 10, 1985General Electric CompanyAcrylated polymers
US4578504 *Jun 3, 1983Mar 25, 1986Minnesota Mining And Manufacturing CompanyContact lenses
US4633003 *Nov 25, 1985Dec 30, 1986Alcon Laboratories, Inc.Siloxane monomers for ophthalmic applications
US4645811 *Apr 2, 1984Feb 24, 1987Oculus Contact Lens CompanyContact lenses nonwettable by proteins comprising an acrylate-siloxane copolymer also containing an acrylic acid and n-(1,1-dimethyl-3-oxobutyl) acrylamide
US4663185 *Jul 19, 1985May 5, 1987General Electric CompanyOptical fibers, release coatings, polysiloxanes
US4665147 *Sep 24, 1984May 12, 1987Loctite CorporationHydrosilation
US4690993 *Dec 31, 1985Sep 1, 1987Alcon Laboratories, Inc.p-(2-Hydroxy hexafluoroisopropyl) styrene [HFIS] monomer for ophthalmic applications
US4711943 *Apr 26, 1985Dec 8, 1987Sola U.S.A. Inc.Improved oxygen permeability and stability
US4783542 *May 25, 1983Nov 8, 1988General Electric CompanySilicone compounds
US4801740 *Feb 13, 1987Jan 31, 1989Minnesota Mining And Manufacturing CompanyAcrylate and methacrylate monomers and polymers
US4861840 *Dec 3, 1986Aug 29, 1989Barnes-Hind, Inc.Novel siloxanyl acrylic monomer and gas-permeable contact lenses made therefrom
US4997897 *Aug 3, 1990Mar 5, 1991Bausch & Lomb IncorporatedUnsaturated esters or amides of aminoanthraquinone dyes
US5055602 *Apr 3, 1990Oct 8, 1991Bausch & Lomb IncorporatedTinting contact lenses blue
US6818719Sep 25, 2001Nov 16, 2004Johnson & Johnson Vision Care, Inc.Polymers and ophthalmic lenses in which they are used
US6822016Sep 6, 2002Nov 23, 2004Johnson & Johnson Vision Care, Inc.Biomedical devices containing internal wetting agents
US6933401 *Jun 30, 2003Aug 23, 2005Frank MolockProcess for the production of vicinal diesters from epoxides
US7052131Sep 6, 2002May 30, 2006J&J Vision Care, Inc.Comprises encapped polysiloxane, polyvinylpyrrolidone, and compatabilizer such as (3-methacryloxy-2-hydroxypropyloxy) propyl-bis(trimethylsiloxy)methylsilane; contact lenses; improved oxygen permeability and wear resistance
US7461937Jan 14, 2005Dec 9, 2008Johnson & Johnson Vision Care, Inc.Soft contact lenses displaying superior on-eye comfort
US7649058Sep 9, 2005Jan 19, 2010Johnson & Johnson Vision Care, Inc.Comprises encapped polysiloxane, polyvinylpyrrolidone, and compatabilizer such as (3-methacryloxy-2-hydroxypropyloxy) propyl-bis(trimethylsiloxy)methylsilane; contact lenses; improved oxygen permeability and wear resistance
US7666921Sep 10, 2004Feb 23, 2010Johnson & Johnson Vision Care, Inc.Biomedical devices containing internal wetting agents
US7691916Mar 30, 2007Apr 6, 2010Johnson & Johnson Vision Care, Inc.Comprises encapped polysiloxane, polyvinylpyrrolidone, and compatabilizer such as mono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butyl terminated polydimethylsiloxane; contact lenses; improved oxygen permeability and wear resistance
US7825170Dec 15, 2008Nov 2, 2010Johnson & Johnson Vision Care, Inc.Contact lenses
US7939579Jul 9, 2008May 10, 2011Contamac LimitedHydrogels and methods of manufacture
US8168720Dec 3, 2009May 1, 2012Johnson & Johnson Vision Care, Inc.Biomedical devices containing internal wetting agents
US8373000Jun 4, 2004Feb 12, 2013Johnson & Johnson Vision Care, Inc.Reacting a substituted epoxide with a lithium salt and acrylic acid to form a substituted hydroxy acrylate; chemical intermediates; ophthalmic devices, soft contact lenses
US8399538Sep 23, 2010Mar 19, 2013Johnson & Johnson Vision Care, Inc.Contact lenses
US8431669Mar 27, 2012Apr 30, 2013Johnson & Johnson Vision Care, Inc.Biomedical devices containing internal wetting agents
US8440738Jan 27, 2012May 14, 2013Timothy HiggsSilicone hydrogels and methods of manufacture
US8450387Mar 30, 2007May 28, 2013Johnson & Johnson Vision Care, Inc.Biomedical devices containing internal wetting agents
US8481608Jan 19, 2010Jul 9, 2013Nof CorporationSilicone monomer
US8580904Mar 5, 2010Nov 12, 2013Nof CorporationSilicone monomer
US8741981Feb 7, 2013Jun 3, 2014Johnson & Johnson Vision Care, Inc.Contact lenses
US8796353Mar 22, 2013Aug 5, 2014Johnson & Johnson Vision Care, Inc.Biomedical devices containing internal wetting agents
US20130085203 *Sep 13, 2012Apr 4, 2013Osamu Tsuchida(meth)acrylic-modified organopolysiloxane, radiation-curable silicone composition, silicone release liner, and making methods
CN1816554BJun 29, 2004Aug 17, 2011庄臣及庄臣视力保护公司Process for the production of bis(trimethylsilyloxy)silylalkylglycerol methacrylates
CN102348726BMar 5, 2010Oct 23, 2013日油株式会社Silicone monomer
DE3542347A1 *Nov 29, 1985Jun 12, 1986Gen ElectricVerfahren zur herstellung acrylat-funktioneller halogensilane und halogensiloxane
EP0130731A2 *Jun 19, 1984Jan 9, 1985Loctite CorporationMethacrylated siloxanes
EP2407493A1 *Mar 5, 2010Jan 18, 2012NOF CorporationSilicone monomer
WO1984000763A1 *Aug 8, 1983Mar 1, 1984Edward ChoSiloxane-containing polymers and contact lenses therefrom
WO2002031007A1 *Sep 25, 2001Apr 18, 2002Kazuhiko FujisawaPolymer and ocular lens comprising the same
WO2005005445A1 *Jun 29, 2004Jan 20, 2005Garner JasonProcess for the production of bis(trimethylsiloxy)silylalkylglycerol methacrylates
Classifications
U.S. Classification556/437
International ClassificationC07F7/08, C08F30/08, G02C7/04, C08F30/00
Cooperative ClassificationC07F7/0852
European ClassificationC07F7/08D4H4F
Legal Events
DateCodeEventDescription
Jun 9, 1993ASAssignment
Owner name: MENICON CO., LTD., JAPAN
Free format text: MERGER;ASSIGNOR:TOYO CONTACT LENS CO., LTD.;REEL/FRAME:006653/0574
Effective date: 19780310